Metallurgy and Foundry Engineering – Vol. 42, 2016, No. 3, pp.

171–178
http://dx.doi.org/10.7494/mafe.2016.42.3.171

Żaneta Kurleto-Kozioł, Beata Grabowska1

Study on the activation of calcium montmorillonite (Ca-MMT)

by sodium cations

Badania nad procesem aktywacji

montmorylonitu wapniowego Ca-MMT kationami sodu

Abstract
The results of spectral research (IR, UV-Vis) on the activation process of calcium montmorillon-
ite Ca-MMT by sodium cations are presented in this article. The modifications of Ca-MMT were
carried out by a modifier in the form of sodium carbonate by keeping different times of activa-
tions. On the basis of received sodium modifiers MMT (Na-MMT) analytical cycle of research was
done, including structural (IR) and spectrophotometric (UV-Vis) research, in order for the designa-
tion of ion exchange ability (CEC). There was observed that the method of processing modifica-
tion (changing activation time) does not affect on ion exchange ability Na-MMT. Application of
modified MMT used as a binding material in greensand will be described in the next part of our
planned research.
Keywords: montmorillonite, activation of montmorillonite, cation exchange capacity, UV-Vis, IR

Streszczenie
W  artykule przedstawiono wyniki badań spektralnych (IR, UV-Vis) procesu aktywacji montmo-
rylonitu wapniowego Ca-MMT kationami sodu. Modyfikację Ca-MMT prowadzono z  udziałem
modyfikatora w postaci węglanu sodu przy zachowaniu różnych czasów aktywacji. Dla otrzyma-
nych modyfikatów sodowych MMT (Na-MMT) przeprowadzono cykl badań analitycznych, w tym
strukturalnych (IR) oraz spektrofotometrycznych (UV-Vis), w  celu oznaczenia ich zdolności wy-
miany jonowej (CEC). Stwierdzono, że sposób prowadzenia modyfikacji (zmiana czasu aktywacji)
nie wpływa istotnie na zdolność do wymiany jonowej Na-MMT. Zastosowanie zmodyfikowanego
MMT jako materiału wiążącego w masach klasycznych zostanie określone w następnej części za-
planowanych prac badawczych.
Słowa kluczowe: montmorylonit, aktywacja montmorylonitu, zdolność do wymiany jonowej,
UV-Vis, IR

Beata Grabowska D.Sc. Ph.D., Żaneta Kurleto-Kozioł M.Sc. Eng.: AGH University of Science and Technology,
Faculty of Foundry Engineering, Krakow, Poland; beata.grabowska@agh.edu.pl

171
1. Introduction
Montmorillonite (MMT) belongs to the group of natural phyllosilicates from clay miner-
als. Each MMT layer is composed of an aluminum-oxygen octahedral sublayer located
between two silicate-oxygen tetrahedral sublayers. Hence, montmorillonite is classified
as the layered aluminosilicates of the 2:1 layer structure. The lack of full compensation
of charges in the layer causes the appearance of a negative charge in the structure. This
negative charge is compensated by the presence of metal cations (for example, Ca2+,
Na+, K+) in the interlayer surfaces next to the water particles. These cations could easily
be replaced by other cations by their ion exchange ability, thus changing the determined
properties of MMT (for example, their adsorption and absorption abilities). Montmoril-
lonite contained in the interlayer surface cations of calcium (Ca-MMT) appears in nature
as an ingredient of calcium bentonite and is widely used as an absorbent, a catalytic car-
rier, an adhesive agent, an addition for medications and food, and (more recently) a poly-
meric nanofiller [1–6]. Literature data also shows the existence of many possibilities of
modifying the MMT structure by physical or chemical means [1, 2, 4–7]. These processes
are mostly performed in order to improve the thermostable and adhesive preferences of
the material, and also to increase its sorption abilities [1, 2, 6, 7]. In casting technology,
activated bentonite containing sodium cations (Na-MMT) obtained from ion exchange
is used. Na-MMT shows greater binding abilities for sand grains, which is important for
applications in molding-sand technology [8, 9].
The purpose of the research described in this paper was to elaborate the binding
materials used in greensands as a  result of Ca-MMT modification by sodium cations.
Ca-MMT modification was processed with the sodium carbonate modifier by keeping
different times of activations.

2. Methodology

2.1. Materials

The materials used in this study were:

– activated bentonite (Bentonite Specjal, ZGM “Zębiec”),
– non-activated bentonite (Bentonite SN, ZGM “Zębiec”),
– sodium carbonate (Na2CO3) by POCH,
– triethylenetetramine by Aldrich,
– CuSO4 (sulfate [VI], copper [II], anhydrous) by MERCK,
– potassium bromide (KBr) by ACROS ORGANICS,
– distilled water by POCH.

172
2.2. Aparature
The aparature used in this study were:
– Spectrometer IR, Digilab Excalibur FTS 3000 Mx with detector DTGS, electrically
cooled,
– VIS ODYSSEY DR/2500 spectrophotometer with automated wave length calibration
Hach industry, range of wave length: 365–880 nm, resolution 1 nm,
– Microcomputer CP-251 pH-meter with automatic temperature compensation sys-
tem Elmetron industry, equipped with combined pH electrode OSH 10-00 type.

2.3. Research methods

– Structural research by Fourier transform infrared spectroscopy (FTIR) – a  benton-
ite sample (2 mg) was added to the weighed KBr (200 mg). Then, this compound
was precisely mixed and placed in a hydraulic press (200 bars of pressure). A spec-
troscopic description of the prepared sample was made by an IR spectrometer in
relation to the KBr sample as spectrum references. The transmission spectra of the
investigated samples were recorded in a range of 4000–400 cm−1 at a resolution of
4 cm−1. A number of scans were selected dependent on the level of the obtained
signal (within 32–64 scans).
– UV-Vis spectrophotometric measurement – water in a ratio of 1:20 was added to
the weighed bentonite sample (200 mg). Then, this compound was dispersed by
ultrasound. To received suspension, 10 ml 0.01M of Cu(II)-triethylenetetramine was
added and by 50 ml of water was fulfilled, after everything was centrifuged until
a clear solution required for photometrical measurement was received. The spectro-
photometric description of the received solution was prepared in a 10-mm absorp-
tion cell when the length of the wave was equal to 620 nm in relation to water as
a zero probe [10].

3. Results and discussion

3.1. The activation process Ca-MMT
The Ca-MMT modifications were prepared by the cation exchange of metals existing
in the interlayer surfaces. In Figure 1, the schema of the prepared process of activated
Ca-MMT using cation exchange is shown.
Ca-MMT modification was based on preparing a ternary mixture that consisted of cal-
cium montmorillonite (60 g), distillated water (12 cm3), and calcium carbonate (1.86 g). The
mixture was subjected to preliminary homogenization (30 min). Then received mixture by
mortar separate and next displace to ceramic crucible, and after that was put to dry (105°C; 1 h)
or was put down for required time (activation time: 30 min; 1 h; 1.37 h; 2 h; 2.5 h; 3 h; 24 h).

173
Demanded activation time, 1.37 h, was the result of data contained in the patent about
the activation of calcium bentonite [11]. After passing the required time of activation, the
samples were placed to dry (105°C, 1 h). Dried samples of MMT were located to analytic
research. The scheme of action for MMT modification is shown in Figure 2.

Fig. 1. Schematic idea of ion exchange

Fig. 2. Schema of Ca-MMT modification process

174
 In the first phase change of pH for MMR before and after modification was defined
and also compared received results with the value of commercial sodium bentonite Spec-
jal (Na-MMTSpecjal) pH. All of the received in the result of activation MMT samples were
characterized by approximated results of pH (approximately 11). In Table 1, the results
of the research of pH for Ca-MMT and for the selected Na-MMT samples are presented.

Table 1. The pH test results

Sample
Ca-MMT Na-MMT0 h Na-MMT1.37 h Na-MMT24 h Na-MMTSpecjal
labeling
Sodium ben-
Sodium benton- Sodium benton- Sodium benton-
tonite prepared
ite comprising ite obtained in ite obtained in
Calcium ben- in the form
Sample Na-MMT, ob- the activation the activation
tonite contain- of Zębiec (no
description tained without process, the process, the
ing Ca-MMT accurate records
the activation activation time: activation time:
of the time of
process 1.37 h 24 h
activation)

pH 10.82 11.02 11.06 11.13 10.98

3.2. Structural research FTIR

In order to define the changes in the MMT structure after the activation process by
ion exchange, spectroscopes research IR were made. A series of spectrums were car-
ried out for inactivated bentonite contained Ca-MMT and activated samples of ben-
tonites, including commercial activated bentonite Specjal (Na-MMTSpecjal). In Figure 3,
shown spectrums of chosen samples of Na-MMT and compared them with spectrums
Ca-MMT and Na-MMTSpecjal. Bands in the approximately 1600 cm−1 wavenumber range
are connected with stretching vibrations Al-OH and Si-OH bonds. Wideband with ap-
proximately 3400 cm−1 maximum correspond with stretching vibrations in -OH group
from water located in interlayer surface, and 1640 cm−1 approximated band is result
of the vibrations in -OH group in adsorbed water. Stretching vibrations in Si-O was as-
signed the band of approximately 1030–1040 cm−1. Below 900 cm−1 wavenumbers oc-
curs bands characteristic for: AlAlOH, AlFeOH, AlMgOH and for bending vibrations. On
the received spectrums could be noticed that in 3400 cm−1 wavenumber for modifier
samples bands are shifted. This fact shows occurring reactions with water in interlayer
surface. Furthermore, all bands after modification changing its intensity. In the case of
a sample-MMT24 h in the IR spectrum, all frequencies are characterized by higher inten-
sity (spectrum 4) compared with the course of the spectra for other samples Na-MMT
(spectrum 2, 3, and 5). This fact is related to the occurrence of ionic reaction in the
interlayer space of MMT.

175
Fig. 3. IR Spectra: 1 – Ca-MMT; 2 – Na-MMT0 h ; 3 – Na-MMT1.37 h ; 4 – Na-MMT24 h ; 5 – Na-MMTSpecjal

Characteristic absorption bands observed in the IR spectra of the investigated sys-

tem are given in Table 2.

Table 2. Characteristic bands in the IR spectra of the investigated system

Ca-MMT Na-MMT0 h Na-MMT1.37 h Na-MMT24 h Na-MMTSpecjal

Ascription
cm−1
ν-OH vibrations occurring
3630 3634 3634 3634 3634 minerals of 2: 1 in an envi-
ronment octahedral Al
3428 3432 3453 3445 3440 ν(H-O-H)
1642 1646 1646 1642 1642 δ(H-O-H)
The presence of carbonate
– 1423 1423 1427 1427
ions CO32-
1044 1040 1040 1031 1040 ν(Si-O) in SiO4 tetrahedron
917 913 917 913 913 δ(Al-Al-OH)

ν – tensile, δ – bending

176
3.3. UV-Vis spectrometric research
Characteristic for the taken aluminosilicate charge of the layer and also a varying com-
pensating cation charge are determined mainly by superficial preferences including free
swelling capacity (FSC) and also by cation exchange capacity (CEC). The CEC is determined
by various analytical methods, but currently, the spectrophotometric technique is widely
used. This method consists of the measurement of absorbance in measuring analytes
that contain samples of the described substance. Currently, the CEC spectrophotometric
description is carried out with the methylene blue or Cu(II)-triethylenetetramine com-
plex. In the given methods, the analytic base is the adsorption effect of methylene blue or
Cu-TET on the aluminosilicate particles. It also turns out, however, that the adsorption of
Cu-TET occurs easier; this is why this method is less time-consuming as compared to the
method with methylene blue. CEC is the parameter that defines the binding preferences
– the higher the CEC, the better the binding preferences are for MMT. In Figure 4, the
results of the CEC are shown for selected samples of Na-MMT, and these are compared
with the results of Ca-MMT and Na-MMTSpecjal. From the shown figure, we can see that the
lowest value CEC was in the case of natural non modified Ca-MMT (65.99 mmol/100 g).
Therefore, the highest value of CEC was in the case of Na-MMT24 h, which is comparable
with the value for Na-MMTSpecjal (78.89 mmol/100 g). Activation time does not significant-
ly change the ability of the ion exchange. Cation exchange reaction occurs practically
throughout the one-hour activation, although the highest ion exchange capacity has the
Na-MMT24 h sample that correlates to the underlying structural analysis (IR). Within 24 h of
activation, it comes to the structural changes associated with the ion-exchange.

79.29 78.89
77.4 77.78

65.99

Ca-MMT Na-MMT(0 h) Na-MMT(1.37 h) Na-MMT(24 h) Na-MMT(Specjal)

Fig. 4. Cation exchange capacity (CEC): Ca-MMT; Na-MMT0  h ; Na-MMT1.37  h ; Na-MMT24  h ;

Na-MMTSpecjal

177
4. Conclusion
The activation process of calcium montmorillonite was carried out while maintaining dif-
ferent activation times. For the obtained Na-MMT modifiers, analytical tests (pH, IR, UV-Vis)
were conducted. Based on the obtained results, it was found that the ion exchange reaction
takes place during the first hour of activation, as evidenced by structural changes (IR) and
the value of ion exchange capacity (CEC). However, the maximum capacity of the ionic ex-
change has the Na-MMT24 h sample that correlates to the underlying structural analysis (IR).
In the next stage, the obtained modifier Na-MMTs will be used as binders in the masses of
classic and will be studied for their selected technological properties. The results obtained
from this research will allow for the determination of the relationship between the activa-
tion time, ion exchange capacity, and technological properties of the mass.

Acknowledgement
The work was supported by the Project AGH No 11.11.170.318/13.

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